WO2010071314A2

WO2010071314A2 - Marble chips for an artificial marble, manufacturing method thereof, and artificial marble comprising same

Info

Publication number: WO2010071314A2
Application number: PCT/KR2009/007275
Authority: WO
Inventors: 손창호
Original assignee: 제일모직 주식회사
Priority date: 2008-12-15
Filing date: 2009-12-07
Publication date: 2010-06-24
Also published as: AU2009327752A1; US8759420B2; KR20100068987A; US20110263783A1; CN102245681B; JP2012512269A; WO2010071314A3; EP2377896A4; KR101172385B1; RU2488562C2; RU2011126658A; CN102245681A; EP2377896B1; JP5400169B2; AU2009327752B2; EP2377896A2

Abstract

The present invention provides marble chips produced by hardening resin compositions containing binders and reactive monomers, wherein said binders contain halogenated alkoxylated diacrylate oligomers. The marble chips of the present invention can be formed into a uniform pattern, regardless of the time taken for hardening or molding. Therefore, an artificial marble using the marble chips of the present invention may have an outer appearance and texture the same as those of engineered stone, and also present thermoformability and workability characteristics which are advantages of an artificial acrylic marble.

Description

Marble chip for artificial marble, its manufacturing method and artificial marble comprising the same

The present invention relates to a marble chip for artificial marble, a manufacturing method thereof and an artificial marble comprising the same. More specifically, the present invention by applying a binder containing a halogenated alkoxylated diacrylate oligomer to the marble chip expressing the pattern of artificial marble, has excellent bonding strength with the base material and the same or similar specific gravity and the same or similar wear with the base material The present invention relates to a marble chip having characteristics, high specific gravity, high refractive index, and high transparency, and an artificial marble comprising the same.

In general, artificial marble is divided into two types, acrylic and unsaturated polyester, depending on the resin (resin). Acrylic acrylic marble has characteristics such as excellent appearance, soft texture, excellent weather resistance, etc., and the demand for various top plates and interior materials is continuously increasing.

Acrylic artificial marble is a syrup mixed with a monomer such as methyl methacrylate and polymethyl methacrylate, and a marble chip that implements an inorganic filler, color, and pattern is mixed with a polymerization initiator. After dissolution, it is usually produced by casting at an appropriate temperature.

Various kinds of marble chips are put to realize various colors and patterns of artificial marble. In particular, the appearance of artificial marble has a big influence on the value of the product due to the nature of the marble chip.

The marble chip may be hardened into a plate by a method similar to acrylic artificial marble, and then crushed to obtain various particle sizes. An acrylic material, which is the same material as the matrix, is usually used.

In recent years, transparent marble chips have been used to give a crude artificial marble a light and refined feel or a jewel-like feel, and the demand is increasing recently.

Artificial marble using a transparent marble chip that has been commercialized to date is manufactured using polymethyl methacrylate (PMMA) resin or unsaturated polyester resin as a marble chip. However, the transparent chips made of PMMA-based resins or unsaturated polyester resins have a specific gravity of 1.15 to 1.24, which is lower than the specific gravity of the matrix, so that when the artificial marble is manufactured, all the transparent chips float to the upper layer so that the surface layer is completely absent. There is a problem that a transparent chip does not exist or uniform chip distribution is impossible. In addition, to manufacture the artificial marble having a transparent chip distribution on the surface portion has the disadvantage that the amount of use of the chip more than about twice the base material, there is another problem that is difficult to adjust the thickness of the artificial marble.

Therefore, in order to increase specific gravity to the level of the base metal, an inorganic filler such as aluminum trihydrate, barium sulfate, silica, or the like should be added. However, when such an inorganic filler is added, transparency is significantly lowered.

Meanwhile, engineered stone in the form of engineered stone, which can be manufactured using natural silica minerals such as quartz, silica sand, and crystal, or transparent chips such as vitrified silica compounds such as glass or molten glass, Although there is an advantage in chip transparency, it cannot be produced in the production of acrylic artificial marble which is a conventional continuous production method due to problems such as chip settling and chip sanding properties.

The reason is that the MOS hardness of the acrylic compound as the base material and the silica and the silica compound as the chip showing the pattern or the pattern is different, so that the smoothness does not come out due to the difference in the sanding properties after the plate is manufactured.

Therefore, the transparent chip of artificial marble should not only have a high refractive index but also adjust specific gravity to the same or similar to the base material so that the chip does not sink without regard to the molding time so that it can have a constant pattern regardless of the hardening time. It is required to have the same abrasiveness and to satisfy both flatness and smoothness after the manufacture of artificial marble.

MEANS TO SOLVE THE PROBLEM In order to solve the said problem, the present inventors harden the binder containing a halogenated alkoxylated diacrylate oligomer, and the resin composition containing a reactive monomer, and are excellent in binding force with a base material, and are the same or similar specific gravity as a base material. Or, it is to develop a marble chip having similar wear characteristics, high specific gravity, high refractive index, and high transparency and artificial marble using the same.

An object of the present invention is to provide a marble chip having a specific gravity of 1.45 to 1.75 and a manufacturing method thereof.

Another object of the present invention is to provide a marble chip and a method of manufacturing the same which can realize a uniform pattern regardless of curing time or molding time.

Still another object of the present invention is to provide a marble chip having excellent transparency and refractive index and a method of manufacturing the same.

It is still another object of the present invention to provide a marble chip and a method of manufacturing the same having a sanding property and a hardness of the matrix.

Still another object of the present invention is to provide a marble chip having excellent bonding force with a base material and a method of manufacturing the same.

Another object of the present invention is to provide a marble chip and a method for manufacturing the same that can exhibit a three-dimensional texture.

It is still another object of the present invention to provide a marble chip and a method of manufacturing the same, which are excellent in pigment dispersibility and bondability with a matrix.

Still another object of the present invention is to provide a marble chip having excellent chemical resistance and a manufacturing method thereof.

Still another object of the present invention is to provide an artificial marble that can have the same appearance and texture as the engineered stone by applying the marble chip.

Still another object of the present invention is to provide an artificial marble capable of continuous production by applying the marble chip.

Still another object of the present invention is to provide an artificial marble having excellent thermal workability by applying the marble chip.

Still another object of the present invention is to provide an artificial marble having excellent smoothness by applying the marble chip.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to a marble chip. The marble chip is formed by curing a resin composition comprising a binder and a reactive monomer, and the binder includes a halogenated alkoxylated di (meth) acrylate oligomer.

In one embodiment, the resin composition may include 50 to 90 parts by weight of the binder and 10 to 50 parts by weight of the reactive monomer. In another embodiment, the binder may further include a halogenated urethane acrylate or a halogenated epoxy acrylate, and a mixture thereof may also be included. The number average molecular weight of the halogenated urethane acrylate may be 900 to 4,000. In addition, the number average molecular weight of the halogenated epoxy acrylate may be 600 to 3,500.

The reactive monomers are aromatic vinyl monomers, aromatic divinyl monomers, dimers thereof, alkyl or halogen substituted aromatic vinyl monomers, C ₁ -C ₂₀ alkyl (meth) acrylates, C ₆ -C ₂₀ aryl (meth) Acrylates, hydroxy-containing (meth) acrylates, glycidyl (meth) acrylates, C ₆ -C ₂₀ arylphthalates, C ₆ -C ₂₀ arylcarbonates, and the like. In specific embodiments, the reactive monomer may be a styrene monomer, bromo styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, and dodecyl. (Meth) acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) Acrylate, methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanedioldi (meth ) Acrylate, 1,3-propylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentylglycol di (meth) acrylate , Diethylene glycol di (meta) Acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl terephthalate, allyl phthalate, diallyl carbonate, divinylbenzene, alpha methylene styrene, alpha methylene styrene dimer , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxyethyl acrylate, glycidyl ( Epoxyacrylate of meta) acrylic acid, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methylpropanedioldi (meth) acrylate, polyethyleneglycol di (meth) acrylate, and these One or more may be selected from the group consisting of mixtures.

The resin composition may further include an additive selected from the group consisting of colorants, antifoaming agents, coupling agents, ultraviolet absorbers, light diffusing agents, polymerization inhibitors, antistatic agents, flame retardants, heat stabilizers, and mixtures thereof.

In another embodiment, the resin composition may further include a second marble chip, and may be in a chip form which is a chip in which a second marble chip is formed inside the marble chip.

In another embodiment, the resin composition may further include a second resin composition having different colors or transparency. The second resin composition comprises a second binder and a second reactive monomer, wherein the second binder is at least one from the group consisting of halogenated alkoxylated di (meth) acrylate oligomers, halogenated urethaneacrylates, halogenated epoxyacrylates Can be selected.

In one embodiment, the marble chip has a specific gravity of 1.45 to 1.75. Preferably, the marble chip has a specific gravity of 1.50 to 1.70.

In the above embodiment, the marble chip may have a refractive index of 1.55 to 1.75 measured by an ABBE refractometer (3T) at a refractive index of 25 ° C.

Another aspect of the invention relates to a method of manufacturing the marble chip. The method includes preparing a resin composition by mixing a reactive monomer with a binder comprising a halogenated alkoxylated di (meth) acrylate oligomer; Curing the resin composition to prepare a cured product; And crushing the cured product.

In one embodiment, the cured product may be crushed to a diameter or the maximum diagonal length of 0.1 to 30 mm. In this case, the metal may be crushed after being deposited on the cured product.

The binder may further include a binder selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates and mixtures thereof.

In addition, an additive selected from the group consisting of a colorant, an antifoaming agent, a coupling agent, an ultraviolet absorber, a light diffusing agent, a polymerization inhibitor, an antistatic agent, a flame retardant, a heat stabilizer, and a mixture thereof may be further added to the resin composition.

In one embodiment, the second marble chip may be further added to the resin composition to manufacture the chip in the form of a chip in which the second marble chip is formed inside the marble chip.

In another embodiment, the second marble chip may be selected from the group consisting of a marble chip, an acrylic artificial marble chip, and an unsaturated ester artificial marble marble chip of the present invention.

In another embodiment, the resin composition may further include a second resin composition having different colors or transparency to form a flow pattern or a multilayer structure. The second resin composition comprises a second binder and a second reactive monomer, wherein the second binder is at least one from the group consisting of halogenated alkoxylated di (meth) acrylate oligomers, halogenated urethaneacrylates, halogenated epoxyacrylates Can be selected. The second resin composition having different colors or transparency may be included in plural.

Another aspect of the present invention relates to an artificial marble comprising a marble chip of the present invention. The artificial marble is made of marble chips dispersed in a matrix. In embodiments, the specific gravity of the matrix may be 1.52 to 1.83, the specific gravity of the marble chip may be 1.45 to 1.75, and the specific gravity difference between the matrix and the marble chip may be 2.0 or less. The matrix may be a cured product of the curable composition comprising an acrylic syrup and an inorganic filler.

Hereinafter, specific contents of the present invention will be described in detail below.

1 is a schematic diagram of an artificial marble using a chip-in-chip marble chip according to the present invention.

2 is a schematic diagram of artificial marble using a multi-layer marble chip according to the present invention.

Marble Chip

The marble chip of the present invention is formed by curing a resin composition comprising a binder and a reactive monomer, and the binder comprises a halogenated alkoxylated diacrylate oligomer.

The halogenated alkoxylated di (meth) acrylate oligomers include brominated alkoxide bisphenol A diacrylate, brominated alkoxide bisphenol A dimethacrylate, chlorolated alkoxide bisphenol A diacrylate, and chloro alkoxylated. Tide bisphenol A dimethacrylate, etc. are mentioned, It is not necessarily limited to this. In addition, it is possible to use various kinds of halogenated alkoxylated di (meth) acrylates depending on the number of repeating units (-OC ₂ H _4- ) and these may be used alone or in combination of two or more thereof. The number average molecular weight of the halogenated alkoxylated di (meth) acrylate oligomer may be 600 to 4,500.

In another embodiment, the binder may further include a halogenated urethane acrylate or a halogenated epoxy acrylate, and a mixture thereof may also be included. The number average molecular weight of the halogenated urethane acrylate may be 900 to 4,000. In addition, the number average molecular weight of the halogenated epoxy acrylate may be 600 to 3,500. If the molecular weight range is less than the cross-linking density per unit volume is high (brittle), the cross-linking density is lowered if it exceeds the molecular weight range is likely to soften and excessively high viscosity may be difficult to handle.

When a mixture of halogenated urethane acrylates or halogenated epoxy acrylates is used in combination, in one embodiment the binder is used in an amount of 2 to 98% by weight of halogenated alkoxylated di (meth) acrylate oligomer and 2 to 98% by weight of halogenated urethane acrylate. Can be used. In another embodiment, the binder may be used in 2 to 98% by weight of halogenated alkoxylated di (meth) acrylate oligomer and 2 to 98% by weight of halogenated epoxyacrylate. In another embodiment, the binder may be used in an amount of 1 to 98% by weight of halogenated alkoxide di (meth) acrylate oligomer, 1 to 98% by weight of halogenated urethane acrylate and 1 to 98% by weight of halogenated epoxy acrylate.

The binder is 50 to 90 parts by weight, preferably 60 to 90 parts by weight, more preferably 70 to 90 parts by weight. The reactive monomer is 10 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 10 to 30 parts by weight. When the content of the binder is less than 50 parts by weight, the high specific neutralization effect is lowered, and when used in excess of 90 parts by weight, the viscosity may be too high, resulting in poor workability.

The reactive monomers are aromatic vinyl monomers, aromatic divinyl monomers, dimers thereof, alkyl or halogen substituted aromatic vinyl monomers, C ₁ -C ₂₀ alkyl (meth) acrylates, C ₆ -C ₂₀ aryl (meth) Acrylates, hydroxy-containing (meth) acrylates, glycidyl (meth) acrylates, C ₆ -C ₂₀ arylphthalates, C ₆ -C ₂₀ arylcarbonates, and the like. Specific examples of the reactive monomers include styrene monomer, bromo styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, and dode Sil (meth) acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth ) Acrylate, methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanediol di ( Meta) acrylate, 1,3-propylene glycol (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,5-pentanedioldi (meth) acrylate, neopentyl glycoldi (meth) acrylic Rate, diethylene glycol di (meta ) Acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl terephthalate, allyl phthalate, diallyl carbonate, divinylbenzene, alpha methylene styrene, alpha methylene styrene Dimer, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxyethyl acrylate, glycidyl Epoxy acrylate, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methylpropanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like of (meth) acrylic acid. . These can be used individually or in mixture of 2 or more types.

The marble chip of the present invention may further include additives such as a colorant, an antifoaming agent, a coupling agent, an ultraviolet absorber, a light diffusing agent, a polymerization inhibitor, an antistatic agent, a flame retardant, and a heat stabilizer. These additives may be included alone or in combination of two or more.

In another embodiment of the present invention may be in the form of a chip which is a chip in which a second marble chip is formed inside the marble chip. 1 is a schematic diagram of an artificial marble using a marble chip of the chip-in-chip form according to the present invention. As shown in FIG. 1, a relatively small marble chip 11A is embedded in the marble chip 1A of the present invention.

In another embodiment of the present invention, a flow pattern or a multilayer structure may be formed on the marble chip. Figure 2 is a schematic diagram of artificial marble using a marble chip of a multi-layer structure according to the present invention. As shown in FIG. 2, a plurality of

layers

21A, 21B, 21C ,, and different in color or transparency may be formed on the marble chip 2A having a multilayer structure.

The marble chip of the present invention has a specific gravity of 1.45 to 1.75. Preferably, the marble chip has a specific gravity of 1.50 to 1.70. In embodiments it may be 1.51 to 1.67. In addition, the marble chip of the present invention may have a refractive index of 1.55 to 1.75 measured by an ABBE refractometer (3T) at 25 ° C.

Marble Chip Manufacturing Method

Another aspect of the invention relates to a method for manufacturing a marble chip. The method includes preparing a resin composition by mixing a reactive monomer with a binder comprising a halogenated alkoxylated di (meth) acrylate oligomer; Curing the resin composition to prepare a cured product; And crushing the cured product.

The resin composition may include a binder and a reactive monomer, and may further include conventional additives such as colorants, antifoaming agents, coupling agents, ultraviolet absorbers, light diffusing agents, polymerization inhibitors, antistatic agents, flame retardants, and heat stabilizers. The colorant includes an inorganic or organic pigment, a dye and the like, and is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the resin composition. In embodiments, it may be used in an amount of 1.0 to 5.0 parts by weight, and in other embodiments, it may be used in an amount of 0.001 to 0.05 parts by weight. In another embodiment may be used in 0.05 to 2.5 parts by weight.

In an embodiment of the present invention, a curing agent may be used when curing the resin composition. The curing agent may be benzoyl peroxide, dicumyl peroxide, butylhydro peroxide, cumylhydro peroxide, butyl butyl peroxymaleic acid, butyl butyl hydroperoxide, acetyl peroxide, lauroyl peroxide, azobisiso A single or a mixture of two or more selected from butylonitrile, azobis dimethylvaleronitrile, a mixture of peroxides with amines or sulfonic acid compounds, saponified salts of peroxides with copper, cobalt, potassium, calcium, zirconium, and zinc. Can be used. The curing agent may be added to 0.03 to 2.5 parts by weight, preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the resin composition. The curing method is not particularly limited, and may be cured in a heat source condition of 50 to 180 ℃. In order to control the curability, an amine or sulfonic acid compound may be added together with the curing agent or a saponified salt of copper, cobalt, potassium, calcium, zirconium, and zinc may be added.

In an embodiment of the present invention, the cured product is crushed to an average diameter of 0.1 to 30 mm, preferably 0.1 to 20 mm. The shredding method can be easily carried out by those skilled in the art.

In another embodiment of the present invention can be broken after depositing a metal such as aluminum or silver on the cured product. Thus, when the metal chip is deposited and the crushed marble chip is added to the artificial marble, it can be more three-dimensional and produce a jewelry-like effect.

In another embodiment of the present invention, the second marble chip may be further added to the resin composition. The second marble chip may be transparent, translucent, or opaque, and a mixture thereof may be used. In a specific embodiment, the second marble chip may use a marble chip manufactured in the present invention, and may use a marble chip obtained by grinding a conventional acrylic or unsaturated ester artificial marble. In this way, the marble chip obtained by further adding the marble chip to the resin composition, curing and pulverizing is in the form of a chip-in-chip, and can produce more various patterns.

In another embodiment of the present invention, the resin composition may further include a second resin composition having different colors or transparency. The second resin composition comprises a second binder and a second reactive monomer, wherein the second binder is at least one from the group consisting of halogenated alkoxylated di (meth) acrylate oligomers, halogenated urethaneacrylates, halogenated epoxyacrylates Can be selected. The second resin composition having different colors or transparency may be included in plural. In addition, the second resin composition may be transparent or opaque. By using two or more kinds of resin compositions having different colors or transparency as described above, it is possible to form a flow pattern or a multilayered structure on a high specific gravity chip. In a specific embodiment, after preparing two or more kinds of resin compositions having different colors from each other, and simultaneously injecting the two or more kinds of resin compositions into a curing conveyor belt, a cured product having a flow pattern is formed, and when the powder is pulverized, a flow pattern is formed. Marble chips can be manufactured.

Artificial Marble

Another aspect of the present invention relates to an artificial marble comprising a marble chip of the present invention. The artificial marble is prepared by curing the curable composition mixed with the marble chip and the resin syrup prepared in a conventional manner. As the resin syrup, an acrylic resin or an unsaturated polyester type may be used, and preferably, an acrylic resin. The curable composition may further include inorganic fillers or conventional additives such as calcium carbonate, aluminum hydroxide, silica, alumina, barium lactate, magnesium hydroxide, and the like. It can be easily carried out by a person who has.

Since the artificial marble of the present invention uses a marble chip having a specific gravity of 1.45 to 1.75, a uniform pattern can be realized regardless of curing time or molding time, and continuous production is possible.

In embodiments, the specific gravity of the matrix may be 1.52 to 1.83, the specific gravity of the marble chip may be 1.45 to 1.75, and the specific gravity difference between the matrix and the marble chip may be 2.0 or less. Preferably the said specific gravity difference is 1.7 or less, More preferably, it is 1.5 or less, Most preferably, it is 1.0 or less.

The artificial marble of the present invention has a structure in which the marble chip is uniformly dispersed in the matrix since the specific gravity difference between the marble chip and the matrix of the marble chip is small.

The matrix may be a cured product of the curable composition comprising an acrylic syrup and an inorganic filler.

In one embodiment, the artificial marble has a structure in which a chip in chip type marble chip is dispersed using a chip in chip type marble chip. 1 is a schematic view of the artificial marble 10 using the chip-in-chip marble chip 1A. In the marble chip 1A of the present invention, a relatively small marble chip 11A is irregularly distributed, and such a chip-in-chip marble chip 1A is dispersed in the matrix 3.

In another embodiment, the artificial marble has a structure in which a marble chip having a multilayer structure is dispersed using a marble chip having a multilayer structure. 2 is a schematic diagram of the artificial marble 20 using the multi-layer marble chip 2A. As shown in FIG. 2, a plurality of

layers

21A, 21B, 21C, ..., which are different in color or transparency, are formed in the marble chip 2A having a multilayer structure, and the marble chip is dispersed in the matrix 3. have.

The surface texture of the artificial marble using the marble chip can produce a surface texture similar to that of the engineered stone and has excellent workability. Therefore, the countertop of the sink countertop of the kitchen, the countertop of the vanity table, the reception desk of a bank and a general store can be used. It can be applied to a wide range of tops and decorative articles.

In addition, the artificial marble may be pulverized and used as a chip-type marble chip having a transparent chip formed therein.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Examples 1-3: Marble Chip Manufacturing

Example 1

0.2 part by weight of benzoyl peroxide and 0.5 part by weight of bis (4-tertarybutylcyclohexyl) peroxydicarbonate in 100 parts by weight of a resin composition consisting of 80 parts by weight of alkoxylated diacrylate and 20 parts by weight of methyl methacrylate. The mixture was cured at 50 ° C. and then crushed to prepare a high specific gravity chip having a specific gravity of 1.608.

Example 2

The same procedure as in Example 1 was carried out except that 0.01 part by weight of phthalocyanine green was added as a color imparting agent. The specific gravity of the manufactured marble chip was 1.609.

Example 3

To 100 parts by weight of a resin composition consisting of 90 parts by weight of alkoxylated diacrylate and 10 parts by weight of styrene monomer, 0.2 parts by weight of benzoyl peroxide and 0.5 parts by weight of bis (4-tertoxycyclohexyl) peroxydicarbonate were mixed. , And cured at 50 ℃ and then crushed to prepare a high specific gravity chip of specific gravity 1.691.

Comparative Example 1

2 parts by weight of trimethylpropanetriacrylate, 0.1 part by weight of normaldodecyl mercaptan, and 1.0 part by weight of benzoyl peroxide are mixed with 100 parts by weight of a solution prepared by dissolving polymethylmethacrylate in methyl methacrylate and cured at 50 ° C. After crushing, PMMA chips having a specific gravity of 1.183 were prepared.

Comparative Example 2

It carried out similarly to Example 1 except having mixed 100 weight part of unsaturated polyester resins (Aekyung Chemical Co., Ltd., TP-145X) and 1.0 weight part of benzoyl peroxides. The specific gravity of the manufactured marble chip was 1.203.

Comparative Example 3

Example 1 except 100 parts by weight of vinyl ester resin (DION-9120, manufactured by Aekyung Chemical Co., Ltd.) and 1.0 part by weight of benzoyl peroxide, prepared by mixing 60 parts by weight of epoxy acrylate oligomer and 40 parts by weight of styrene monomer. Was performed in the same manner. The specific gravity of the manufactured marble chip was 1.194.

Examples 4 to 6: Preparation of artificial marble

Example 4

180 parts by weight of aluminum hydroxide, 2 parts by weight of trimethylpropanetriacrylate, 0.1 part by weight of normaldodecyl mercaptan, 0.1 part by weight of an antifoaming agent and a dispersant, respectively, in 100 parts by weight of a syrup made by dissolving polymethylmethacrylate in methyl methacrylate. And 50 parts by weight of the marble chip prepared in Example 1 was added to the composition mixed with 1.0 parts by weight of benzoyl peroxide, and stirred well, followed by curing at a temperature of 60 ° C. by a continuous molding method to prepare artificial marble.

Example 5

The same procedure as in Example 4 was carried out except that the colored transparent chip prepared in Example 2 was used.

Example 6

The same procedure as in Example 4 was carried out except that the chip prepared in Example 3 was used.

Comparative Example 4

The same procedure as in Example 4 was performed except that the chip prepared in Comparative Example 1 was used.

Comparative Example 5

The same procedure as in Example 4 was carried out except that the chip prepared in Comparative Example 2 was used.

Comparative Example 6

The same procedure as in Example 4 was carried out except that the chip prepared in Comparative Example 3 was used.

Evaluation of the artificial marbles of Examples 4 to 6 manufactured from the marble chips of Examples 1 to 3 and the comparative marbles of Comparative Examples 4 to 6 prepared from the chips of Comparative Examples 1 to 3 is shown in Table 1 below.

Table 1

Property evaluation method in the above was carried out in the following manner.

(1) Chemical resistance: 1.0 N concentration of hydrochloric acid and 1.0 N concentration of ammonia was evaluated for the surface after immersion for 48 hours in a 25 ℃ environment.

(2) Refractive index: It measured by ABBE refractometer (3T) on 25 degreeC temperature conditions.

(3) Smoothness: The smoothness of the interface between the chip and the base metal after sanding was visually evaluated.

(4) Sanding property: The appearance of the chip after sanding with sandpaper was visually evaluated.

(5) Concave: The interface between the chip and the matrix is cracked, or the chip is decayed and evaluated visually.

(6) Thermal processability: When the artificial marble was heated at 180 ° C. for 20 minutes and the curved surface was processed, the minimum radius that the chip was not protruded or cracked was measured.

As shown in Table 1, Examples 4 to 6 were good in all the physical properties evaluation, and even in the heat workability was good to the curved surface of the radius 150MM. Comparative Example 4 had the best result in the thermal workability, but the transparent chip distribution was not constant at the shear plane. In addition, since the refractive index was low, the texture such as quartz could not be represented, and thus it was impossible to produce the engineered stone. In Comparative Example 5, the chip distribution was poor, the occurrence of concave phenomenon and the thermal processing were found to be the lowest, and the chip was poor in chemical resistance. Comparative Example 6 is not applicable to continuous production because the shear chip distribution is not constant.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims

A marble chip formed by curing a resin composition comprising a binder and a reactive monomer, wherein the binder comprises a halogenated alkoxylated di (meth) acrylate oligomer.
The marble chip of claim 1, wherein the resin composition comprises 50 to 90 parts by weight of the binder and 10 to 50 parts by weight of the reactive monomer.
The marble chip of claim 2, wherein the binder further comprises a binder selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates, and mixtures thereof.
The marble chip of claim 3, wherein the number average molecular weight of the halogenated urethane acrylate is 900 to 4,000, and the number average molecular weight of the halogenated epoxy acrylate is 600 to 3,500.
The method of claim 1, wherein the reactive monomer is a styrene monomer, bromo styrene, vinyl toluene, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate , Dodecyl (meth) acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (Meth) acrylate, methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanediol Di (meth) acrylate, 1,3-propylene glycol (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,5-pentanedioldi (meth) acrylate, neopentylglycol di (meth ) Acrylate, diethylene glycol di (meta ) Acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl terephthalate, allyl phthalate, diallyl carbonate, divinylbenzene, alpha methylene styrene, alpha methylene styrene Dimer, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaacetitol hexa (meth) acrylate, ethoxyethyl acrylate, glycidyl Epoxyacrylates of (meth) acrylic acid, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methylpropanedioldi (meth) acrylate, polyethylene glycol di (meth) acrylate and these Marble chip, characterized in that selected from the group consisting of.
The method of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of colorants, antifoams, coupling agents, ultraviolet absorbers, light diffusing agents, polymerization inhibitors, antistatic agents, flame retardants, heat stabilizers and mixtures thereof. Marble chip made with.
The marble chip of claim 1, wherein the resin composition further comprises a second marble chip, wherein the resin composition is a chip in which a second marble chip is formed inside the marble chip.
The method of claim 1, wherein the resin composition further comprises a second resin composition of different colors or transparency, the second resin composition comprises a second binder and a second reactive monomer, the second binder is alkoxy halide Marble chip, characterized in that at least one selected from the group consisting of a tide di (meth) acrylate oligomer, halogenated urethane acrylate, halogenated epoxy acrylate.
The marble chip of claim 1, wherein the marble chip has a specific gravity of 1.45 to 1.75.
The marble chip according to claim 1, wherein the marble chip has a refractive index of 1.55 to 1.75 measured by an ABBE refractometer (3T) at a refractive index of 25 ° C.
Preparing a resin composition by mixing a reactive monomer with a binder including a halogenated alkoxylated di (meth) acrylate oligomer;

Curing the resin composition to prepare a cured product; And

Crushing the cured product;

Marble chip manufacturing method characterized in that consisting of.
12. The method of claim 11, wherein the cured product is a marble chip manufacturing method, characterized in that crushing the diameter or the maximum diagonal length of 0.1 to 30 mm.
The method of claim 11, wherein the chip is crushed after depositing a metal on the cured product.
The marble chip of claim 11, wherein the binder further comprises a binder selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates, and mixtures thereof.
12. The additive according to claim 11, further comprising a colorant, an antifoaming agent, a coupling agent, an ultraviolet absorber, a light diffusing agent, a polymerization inhibitor, an antistatic agent, a flame retardant, a heat stabilizer, and a mixture thereof. Marble chip manufacturing method.
The method of claim 11, wherein the second chip is further added to the resin composition to manufacture the chip as a chip having a second chip formed inside the chip.
The method of claim 16, wherein the second marble chip is selected from at least one selected from the group consisting of the marble chip of any one of claims 1 to 10, acrylic artificial marble marble chips, unsaturated ester artificial marble marble chips. Marble chip manufacturing method.
The method of claim 11, wherein the resin composition further comprises a second resin composition having a different color or transparency, the second resin composition comprises a second binder and a second reactive monomer, the second binder is alkoxy halide A method for manufacturing a marble chip, characterized in that at least one selected from the group consisting of a tide di (meth) acrylate oligomer, a halogenated urethane acrylate and a halogenated epoxy acrylate to form a flow pattern or a multilayer structure.
The method of claim 18, wherein the second resin composition having different colors or transparency comprises a plurality of marble chip manufacturing methods.
Artificial marble comprising a marble chip of any one of claims 1 to 10.
The artificial marble according to claim 20, wherein the artificial marble is formed by dispersing marble chips in a matrix.
The artificial marble of claim 21, wherein the matrix has a specific gravity of 1.52 to 1.83, a marble chip having a specific gravity of 1.45 to 1.75, and a specific gravity difference between the matrix and the marble chip of 2.0 or less.
23. The artificial marble according to claim 22, wherein the matrix is a cured product of a curable composition comprising an acrylic syrup and an inorganic filler.